CN1830559A - New type resin catalyst for making 3-hydroxy inner aldehyde from acrolein hydration and its application - Google Patents
New type resin catalyst for making 3-hydroxy inner aldehyde from acrolein hydration and its application Download PDFInfo
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- CN1830559A CN1830559A CN 200610025210 CN200610025210A CN1830559A CN 1830559 A CN1830559 A CN 1830559A CN 200610025210 CN200610025210 CN 200610025210 CN 200610025210 A CN200610025210 A CN 200610025210A CN 1830559 A CN1830559 A CN 1830559A
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Abstract
A chelated ion exchange resin catalyst for preparing 3-hydroxypropanal from acrolein by hydrating reaction has a surface layer carrying amidocarboxylic acid groups and a basic body which is a three-element copolymer styrene-divinylbenzene- (methyl) acrylate (or acrylonitrile). It has low reaction temp and high conversion rate and selectivity.
Description
Technical field
The catalyst of the acrolein hydration system of the present invention relates to 3-hydroxy propanal relates in particular to the preparation of stinging the mould assembly ion-exchange resin catalyst and the application of acrolein hydration system 3-hydroxy propanal.
Background technology
1, ammediol (1,3-PDO) carrying out the PTT (PTT) that polymerisation generates with the terephthalic acid (TPA) methyl esters is a kind of novel macromolecular material, the fiber of being made by PTT not only has good resilience, bulkiness, chromatophilia, and have advantages such as inherent pollution resistance, antistatic behaviour, be a kind of macromolecular material that has development prospect.Though PTT just came out in the fifties, because of its main monomer 1, ammediol can't be realized industrialization, makes the development of PTT stay cool all the time for many years.In recent years, along with 1, the success of 3-PDO suitability for industrialized production, the Application and Development of PTT has received concern again.With methacrylaldehyde is raw material hydration hydrogenation preparing 1, and 3-PDO is one of successful suitability for industrialized production route.And acrolein hydration to prepare the 3-hydroxy propanal be methacrylaldehyde preparation 1, the important step of 3-PDO.Because methacrylaldehyde is very unstable, prepare in the process of 3-hydroxy propanal at acrolein hydration, be easy to the addition of methacrylaldehyde and 3-hydroxy propanal, the side reactions such as oligomerisation of methacrylaldehyde, and these reaction meetings aggravate along with the rising of temperature, the accessory substance that is generated can deposit on ion-exchange resin catalyst gradually, cause the catalyst bed layer resistance to increase and the acrolein conversion rate reduction, thereby shortened the service life of catalyst.Therefore, seek a kind of efficient and good catalyst of selectivity is the emphasis that acrolein hydration prepares 3-hydroxy propanal technical study always.
U.S. Pat 2,434,110 reports, methacrylaldehyde obtains the 3-hydroxy propanal through hydration reaction under the effect of inorganic acid catalysts such as sulfuric acid, hydrochloric acid.Use the aqueous acrolein solution of 5%-30% at high temperature to finish reaction through catalysis.The shortcoming of this technology is that the yield of 3-hydroxy propanal is low, shows as methacrylaldehyde especially to the selection dependence of acidic catalyst and the unstability of reaction intermediate.European patent EP-A 0 487 903 reports, methacrylaldehyde also can pass through phosphoric acid or dihydrogen orthophosphate catalysis hydration, if but can not make troubles to hydrogenation reaction subsequently the Ex-all after hydration of phosphoric acid class catalyst.U.S. Pat 3,536,763 reports under 40～120 ℃ condition, use the weak-acid cation-exchange resin catalyst, and the 3-hydroxy propanal yield that obtains can reach 80%, and the general conversion ratio of methacrylaldehyde is in the scope of 25%-65%.Yet this catalyst is not suitable for industrial production, because this catalyst need react under hot conditions for a long time, the space-time yield and the selectivity of reaction are low.U.S. Pat 5,015, proposing a kind of styrene-divinylbenzene in 789 is that matrix surface contains-NH-CH
2-PO
3H
2The chelating ion exchange resin catalyst of functional group, U.S. Pat 5,171 adopts in 898 a kind of surface to contain-CH
2-N-(CH
2COOH)
2The chelating ion exchange resin catalyst of functional group, this two classes chelating ion exchange resin all shows the selectivity of higher acrolein conversion rate and 3-hydroxy propanal in the acrolein hydration course of reaction, but because this two classes catalyst all exists the life cycle weak point, characteristics such as cubical contraction is big in the catalyst transformation process also are not suitable for industrial production.Adopt among the CN1345713 a kind of styrene-divinylbenzene be matrix surface have a thiodiglycolic acid amine functional group sting the mould assembly ion-exchange resin catalyst, reaction temperature is in the time of 50～60 ℃, acrolein conversion rate is 82～87%, and 3-hydroxy propanal selectivity is 82～91%.Adopt among the CN1369471 a kind of styrene-divinylbenzene be matrix the rare earth ion exchange contain carboxylic acid sting the mould assembly ion-exchange resin catalyst, in reactant liquor, add mass fraction and be 1 of 0.15% propionic acid and 2.5%, ammediol, when reaction temperature is 60 ℃, acrolein conversion rate is 83.2%, and the overall selectivity of 3-hydroxy propanal and dimer thereof is 93.0%.In sum as can be seen, acrolein hydration prepares the problems such as method all the ubiquity reaction temperature is higher, air speed is lower, catalyst selectivity difference of 3-hydroxy propanal at present, thereby is unfavorable for the industrial applications of this method.
Summary of the invention
The object of the present invention is to provide a kind of method of acrolein hydration system 3-hydroxy propanal, the catalyst that adopts this method to provide, the reasonable big problem of catalyst cubical contraction in transformation process that solved, and acrolein hydration is reflected at when carrying out under the lower reaction temperature, obtain higher acrolein conversion rate and excellent 3-hydroxy propanal selectivity, thereby solved the problem that prior art exists effectively.
The present invention is achieved by the following technical solutions:
Use a kind of surface to have macropore styrene-divinylbenzene-acrylate, methacrylate, acrylonitrile or the methacrylonitrile ternary terpolymer chelating ion exchange resin catalyst of acid amides carboxylic acid functional, catalyzing propone aldehyde and water reaction generate the 3-hydroxy propanal.This catalyst surface contains the functional group just like molecular structure shown in (I):
Wherein, R1=hydrogen or-(CH
2)
mCOOH, m=0,1,2,3; R2=-(CH
2)
nCOOH, n=0,1,2,3.Resin catalyst need carry out following preliminary treatment: earlier with after the containing stinging of acid amides carboxylic acid functional and close ion exchange resin and become h type resin with 1N hydrochloric acid or sulfuric acid acidation of sodium type, with deionized water chlorion or sulfate ion are cleaned, sodium hydrate aqueous solution with 5 weight % soaked 5～10 hours again, and then make the transition with 1N hydrochloric acid or sulfuric acid, so triplicate is converted into Hydrogen at last fully.After fully h type resin carries out the part exchange with the aqueous metal salt of 0.1～0.5 weight % concentration, be washed till neutral afterwards standby with deionized water.Hydrogen on the resin catalyst acid functional group can partly exchange with alkali metal, alkaline-earth metal or rare earth ion, and the exchange capacity of metal ion is 0～15%, and preferred 5～10%.Reaction process condition is: the mass fraction of aqueous acrolein solution is 5～20%, preferred 10～15%; The acrolein hydration reaction temperature is 30～80 ℃, preferred 40～60 ℃; The acrolein hydration reaction velocity is 0.2～3.0h
-1, preferred 0.5～1.5h
-1The acrolein hydration reaction pressure is 0.1～1.5MPa, preferred 0.1～0.5MPa.Add carboxylic acid in the aqueous acrolein solution and regulate the pH value, the carboxylic acid that is added is C
2～C
8Aliphatic carboxylic acid a kind of, preferred propionic acid or acrylic acid.The carboxylic acid that is added is 100ppm～20000ppm by weight, preferred 500ppm～5000ppm; The pH value of aqueous acrolein solution is 2～6, preferred 3～5.Need to add polymerization inhibitor in the aqueous acrolein solution, polymerization inhibitor is hydroquinones (being called for short HQ), p methoxy phenol (being called for short MQ), 2,2,6,6-tetramethyl-4-hydroxy piperidine NO free radical (being called for short ZJ-701), tricresyl phosphite (2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical) a kind of in the ester (be called for short ZJ-705) or their compound, the addition of polymerization inhibitor is 100～1000ppm.
Adopt method of the present invention, can under lower reaction temperature, generate the 3-hydroxy propanal by acrolein hydration by highly selective.
The specific embodiment
To be illustrated with specific embodiment below, but content of the present invention is not limited to these embodiment.
Embodiment 1～8
The preliminary treatment of catalyst: after the styrene-divinylbenzene that contains the acid amides carboxylic acid functional-(methyl) acrylate of sodium type or methacrylonitrile ternary polymerization chelating ion exchange resin become h type resin with 1N hydrochloric acid or sulfuric acid acidation, with deionized water chlorion or sulfate ion are cleaned, sodium hydrate aqueous solution with 5 weight % soaked 5～10 hours again, and then make the transition with IN hydrochloric acid or sulfuric acid, triplicate like this, after at last the resin of complete Hydrogen being carried out the part exchange with the aqueous metal salt of 0.1～0.5 weight % concentration, it is standby to be washed till neutral back with deionized water.Determine the amount of exchange metal ion by the sour exchange capacity of measuring complete h type resin and part exchanger resin.
Reaction evaluating: in the stainless steel fixed bed reactors of φ 14mm * 300mm, pack into through the resin catalyst 20g of above-mentioned processing, the reactor outside is incubated with circulating hot water, presses 0.5～1.5h with measuring pump
-1Reaction velocity be that 10～15% aqueous acrolein solution is squeezed in the reactor with mass fraction, the addition of polymerization inhibitor HQ, MQ, ZJ-701 or ZJ-705 is 500～1000ppm in the aqueous acrolein solution, propionic acid or acrylic acid addition are 500～1000ppm, under 40～55 ℃, normal pressure, carry out the acrolein hydration reaction, concrete catalyst type among each embodiment, reaction condition and reaction 50 hours the results are shown in Table 1.
The surface functional group of table 1 resin catalyst and be used for the condition and the result of acrolein hydration reaction
| Title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Reaction temperature, ℃ | 40 | 40 | 40 | 50 |
| The methacrylaldehyde mass fraction, % | 12.0 | 15.0 | 10.0 | 12.0 |
| Reaction velocity, h -1 | 1.2 | 1.5 | 1.0 | 1.2 |
| Polymerization inhibitor | HQ | HQ+ZJ-705 | HQ+ZJ-701 | HQ |
| The polymerization inhibitor amount, ppm | 500 | 500 | 500 | 1000 |
| Aliphatic acid | Propionic acid | Acrylic acid | Acrylic acid | Acrylic acid |
| The aliphatic acid amount, ppm | 500 | 500 | 1000 | 1000 |
| R1 in the resin surface functional group | -COOH | -CH 2-COOH | -CH 2-CH 2-COOH | -CH 2-CH 2-COOH |
| R2 in the resin surface functional group | -CH 2-COOH | -CH 2-COOH | -CH 2-COOH | -CH 2-CH 2-COOH |
| Species of metal ion | - | - | Na | Ca |
| The metal ion exchanged amount, % | 0 | 0 | 3 | 5 |
| Acrolein conversion rate, % | 61.2 | 65.3 | 66.8 | 72.4 |
| 3-hydroxy propanal selectivity, % | 96.0 | 96.7 | 97.5 | 96.4 |
Table 2.
| Title | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Reaction temperature, ℃ | 50 | 50 | 55 | 55 |
| The methacrylaldehyde mass fraction, % | 12.0 | 15.0 | 12.0 | 15.0 |
| Reaction velocity, h -1 | 1.2 | 1.5 | 1.2 | 1.0 |
| Polymerization inhibitor | HQ | ZJ-701 | MQ | MQ+ZJ-701 |
| The polymerization inhibitor amount, ppm | 500 | 1000 | 800 | 1000 |
| Aliphatic acid | Propionic acid | Propionic acid | Acrylic acid | Acrylic acid |
| The aliphatic acid amount, ppm | 800 | 800 | 800 | 500 |
| R1 in the resin surface functional group | -CH 2-COOH | -CH 2-CH 2-COOH | -CH 2-CH 2-COOH | -CH 2-COOH |
| R2 in the resin surface functional group | -CH 2-COOH | -CH 2-COOH | -CH 2-CH 2-COOH | -CH 2-COOH |
| Species of metal ion | Na | Mg | La | Mg |
| The metal ion exchanged amount, % | 8 | 10 | 5 | 5 |
| Acrolein conversion rate, % | 74.1 | 73.5 | 70.3 | 75.5 |
| 3-hydroxy propanal selectivity, % | 95.3 | 95.9 | 97.3 | 93.6 |
The comparative example 1
The polystyrene chelating ion exchange resin (TP-208 of Bayer company) that the surface is had the iminodiacetic acid (salt) acid functional group is exchanged into Hydrogen, in the fixed bed reactors of packing into, presses 1.2h with measuring pump then
-1Reaction velocity be that 15% aqueous acrolein solution is squeezed in the reactor with mass fraction, the addition of polymerization inhibitor HQ and ZJ-701 is 500ppm in the aqueous acrolein solution, under 50 ℃, normal pressure, carry out the acrolein hydration reaction, the conversion ratio of methacrylaldehyde is 67.5%, and the selectivity of 3-hydroxy propanal is 88.5%.
The comparative example 2
The polystyrene that the surface is had imino group phosphoric acid functional group is stung mould assembly ion exchange resin (Rohm﹠amp; The Dulite C467 of Haas company) is exchanged into Hydrogen, in the fixed bed reactors of packing into, presses 1.2h with measuring pump then
-1Reaction velocity be that 15% aqueous acrolein solution is squeezed in the reactor with mass fraction, the addition of polymerization inhibitor HQ and ZJ-701 is 500ppm in the aqueous acrolein solution, under 50 ℃, normal pressure, carry out the acrolein hydration reaction, the conversion ratio of methacrylaldehyde is 49.0%, and the selectivity of 3-hydroxy propanal is 93.0%.
Claims (9)
1, a kind of resin catalyst of acrolein hydration system 3-hydroxy propanal, it is characterized in that this catalyst is the macropore chelating ion exchange resin that a kind of styrene-divinylbenzene-acrylate, methacrylate, acrylonitrile or methacrylonitrile ternary polymerization form, its surface contains the amido-carboxylic acid group just like structure shown in (I):
Wherein, R1=hydrogen or-(CH
2)
mCOOH, m=0,1,2 or 3; R2=-(CH
2)
nCOOH; N=0,1,2 or 3.
2, the preparation method of resin catalyst according to claim 1, it is characterized in that this catalyst need carry out following preliminary treatment: after the first chelating ion exchange resin that contains the acid amides carboxylic acid functional with the sodium type becomes h type resin with 1N hydrochloric acid or sulfuric acid acidation, with deionized water chlorion or sulfate ion are cleaned, sodium hydrate aqueous solution with 5 weight % soaked 5～10 hours again, and then with 1N hydrochloric acid or sulfuric acid acidation three times, making the transition is complete h type resin.
3, the preparation method of resin catalyst according to claim 1 and 2, it is characterized in that the hydrogen in this catalyst acid functional group can carry out the part ion exchange with the aqueous metal salt of 0.1～0.5 weight % concentration, and being washed till neutrality with deionized water, the exchange capacity that makes metal ion is 0～15%.
4, the preparation method of resin catalyst according to claim 3, the slaine that it is characterized in that preparing this catalyst is alkali metal, alkaline-earth metal or the rare earth metal salt of solubility, the metal ion exchanged amount is 5～10%.
5, the application of resin catalyst according to claim 1 is characterized in that the condition that this catalyst is applied to acrolein hydration reaction system 3-hydroxy propanal is: the mass fraction 5～20% of aqueous acrolein solution, 30～80 ℃ of temperature, air speed 0.2～3.0h
-1, pressure 0.1～1.5MPa.
6, the application of resin catalyst according to claim 5, the mass fraction that it is characterized in that aqueous acrolein solution is 10～15%, and reaction temperature is 40～60 ℃, and reaction velocity is 0.5～1.5h
-1, reaction pressure is 0.1～0.5MPa.
7, the application of resin catalyst according to claim 5 is characterized in that can adding in the aqueous acrolein solution carboxylic acid and regulates the pH value, and the carboxylic acid that is added is C
2～C
8Aliphatic carboxylic acid a kind of, addition is 100ppm～20000ppm, pH value of aqueous solution is 2～6.
8, the application of resin catalyst according to claim 7 is characterized in that the carboxylic acid that is added is propionic acid or acrylic acid, and addition is 500ppm～5000ppm, and pH value of aqueous solution is 3～5.
9, the application of resin catalyst according to claim 1 or 5, it is characterized in that needing in the aqueous acrolein solution to add polymerization inhibitor, polymerization inhibitor is hydroquinones, p methoxy phenol, 2,2,6,6-tetramethyl-4-hydroxy piperidine NO free radical, tricresyl phosphite (2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical) a kind of in the ester or their compound, the addition of polymerization inhibitor is 100～1000ppm.
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|---|---|---|---|
| CNB2006100252101A CN100417443C (en) | 2006-03-29 | 2006-03-29 | New type resin catalyst for making 3-hydroxy inner aldehyde from acrolein hydration and its application |
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|---|---|---|---|
| CNB2006100252101A CN100417443C (en) | 2006-03-29 | 2006-03-29 | New type resin catalyst for making 3-hydroxy inner aldehyde from acrolein hydration and its application |
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| CN110204422A (en) * | 2019-07-01 | 2019-09-06 | 宁波环洋新材料股份有限公司 | A method of 1,3- propylene glycol is prepared by methacrylaldehyde |
| CN112062663A (en) * | 2019-06-11 | 2020-12-11 | 万华化学集团股份有限公司 | Method for preparing 3-hydroxypropionaldehyde by acrolein hydration |
| CN113105315A (en) * | 2021-04-14 | 2021-07-13 | 上海师范大学 | Method for synthesizing high-concentration 3-hydroxypropionaldehyde by continuous catalytic reaction |
| CN114392768A (en) * | 2022-01-13 | 2022-04-26 | 江苏扬农化工集团有限公司 | Catalyst for preparing hydroxy aldehyde by olefine aldehyde hydration and method thereof |
| CN114392772A (en) * | 2022-01-13 | 2022-04-26 | 江苏扬农化工集团有限公司 | Aminophenyl acidic chelate resin catalyst, preparation method and application thereof in olefine aldehyde hydration |
| CN115784862A (en) * | 2022-12-07 | 2023-03-14 | 万华化学集团股份有限公司 | Method for preparing 3-hydroxypropionaldehyde by acrolein hydration |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3926136A1 (en) * | 1989-08-08 | 1991-02-14 | Degussa | METHOD FOR PRODUCING 1,3-PROPANDIOL |
| DE4038192A1 (en) * | 1990-11-30 | 1992-06-04 | Degussa | PROCESS FOR PREPARING 1,3-PROPANDIOL |
| US6284930B1 (en) * | 1999-07-30 | 2001-09-04 | E.I. Du Pont De Nemours And Company | Process for the preparation of 3-hydroxypropanal |
| CN1148340C (en) * | 2000-09-26 | 2004-05-05 | 上海石油化工股份有限公司 | Catalyst for preparing 3-hydroxy-propionaldehyde by acroleic hydration |
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2006
- 2006-03-29 CN CNB2006100252101A patent/CN100417443C/en active Active
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| CN112062663B (en) * | 2019-06-11 | 2022-04-22 | 万华化学集团股份有限公司 | Method for preparing 3-hydroxypropionaldehyde by acrolein hydration |
| CN110204422A (en) * | 2019-07-01 | 2019-09-06 | 宁波环洋新材料股份有限公司 | A method of 1,3- propylene glycol is prepared by methacrylaldehyde |
| CN110204422B (en) * | 2019-07-01 | 2022-06-10 | 宁波环洋新材料股份有限公司 | Method for preparing 1, 3-propylene glycol from acrolein |
| CN113105315A (en) * | 2021-04-14 | 2021-07-13 | 上海师范大学 | Method for synthesizing high-concentration 3-hydroxypropionaldehyde by continuous catalytic reaction |
| CN113105315B (en) * | 2021-04-14 | 2023-09-22 | 上海师范大学 | Method for synthesizing high-concentration 3-hydroxy-propanal by continuous catalytic reaction |
| CN114392768A (en) * | 2022-01-13 | 2022-04-26 | 江苏扬农化工集团有限公司 | Catalyst for preparing hydroxy aldehyde by olefine aldehyde hydration and method thereof |
| CN114392772A (en) * | 2022-01-13 | 2022-04-26 | 江苏扬农化工集团有限公司 | Aminophenyl acidic chelate resin catalyst, preparation method and application thereof in olefine aldehyde hydration |
| CN114392772B (en) * | 2022-01-13 | 2023-08-01 | 江苏扬农化工集团有限公司 | Aminophenyl acidic chelating resin catalyst, preparation method and application thereof in olefine aldehyde hydration |
| CN114392768B (en) * | 2022-01-13 | 2023-11-10 | 江苏扬农化工集团有限公司 | Catalyst for preparing hydroxyaldehyde by olefine aldehyde hydration and method thereof |
| CN115784862A (en) * | 2022-12-07 | 2023-03-14 | 万华化学集团股份有限公司 | Method for preparing 3-hydroxypropionaldehyde by acrolein hydration |
| CN115784862B (en) * | 2022-12-07 | 2023-12-19 | 万华化学集团股份有限公司 | Method for preparing 3-hydroxy-propanal by hydration of acrolein |
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Effective date of registration: 20170215 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |